Production of normal alpha, omega-dicyanoalkanes



States 3,329,704 PRODUCTION OF NORMAL agar-DI- CYANOALKANES Charles V. Goebel, .lr., 17 Constitution Drive, Corte Madera, Calif. 94925, and Louis L. Ferstadig, 2548 Tassajara Ave., El Cerrito, Calif. 94530 No Drawing. Filed Apr. 7, 1964, Ser. No. 358,079

2 Claims. (Cl. 260-4658) This invention relates to a process for the production of 1,8-dibromooctane. More particularly, it relates to a process for the production of l,8dibromooctane in which a treated cyclooctene vapor phase thermal crackate is converted to substantially pure 1,8-dibromooctane by the addition of hydrogen bromide to an acid-treated cyclooctene crackate in the presence of a di-t-alkyl peroxide catalyst at low temperatures.

Cyclooctene is known to be cleaved under vapor phase thermal cracking conditions. The resulting product mixture upon distillation yields a cyclooctene heart-cut crackate of substantial purity, 97% and higher, which is useful as an intermediate for many purposes. Despite its high purity, however, it has been found to respond poorly when used for a free radical catalyzed addition of hydrogen bromide thereto. Normally a pure diolefin feed can yield from about 95 to 100% primary alkyl bromide. The 97% pure cyclooctene crackate, however, yields only about 75% primary dibromide, with the balance being 1,7- and 2,7-dibromooctane and tarry byproduct. All or a portion of the 3% impurity appears to be promoting at least a corresponding 7-fold byproduct formation.

It has now been found that liquid phase contacting of heart-cut vapor phase cyclooctene crackate with 88 to 97% sulfuric acid at a temperature below about 10 C. effectively destroys trace impurities responsible for interfering byproduct-forming reactions when the untreated crackate is reacted under catalytic-free radical conditions with hydrogen bromide. For each volume of feed, about 0.005 to 0.05 volume of the acid is used. After no more than about 10 minutes contact time, the acid phase is separated from the diene hydrocarbon which may then be effectively converted to the desired dibromide in an essentially quantitative yield.

1,8-dibromooctane is especially useful as an intermediate in the preparation of sebaconitrile, a,w-decamethylenediamine, sebacic acid and 1,8-dihydroxyoctane.

By cyclooctene heart-cut crackate is meant, in general, the thermally cracked cyclooctene product as obtained from the vapor phase thermal cracking of cyclooctene at a temperature in the range 520 to 575 0., preferably at about 530 to 550 C., as a result of rather short contact times, preferably less than about 15 seconds which has been topped by distillation to remove components boiling at one atmosphere below about 96 C.

By catalytic-free radical generating conditions in the present context is meant, in general, the contacting of hydrogen bromide with an alkadiene in the liquid phase in the presence of a homolytically dissociable organic compound at dissociation temperatures in the range from about l to about 40 C. and the equivalent.

In accordance with the present inventive process, one liquid volume of heart-cut crackate is contacted efiiciently with from about 0.005 to 005 volume of about 90% aqueous sulfuric acid. The contacting is for a reasonably short period-for less than about minutes and, preferably, for less than five minutes-in view of the reactive nature of diene hydrocarbons.

The sulfuric acid-treated liquid hydrocarbon phase is then separated from the acid phase and washed. Preferably, the washing is accomplished by two water and one dilute aqueous alkali washes, for example, 5% aqueous sodium hydroxide solution or the equivalent, which is applied intermediate the two water washes. While the treated crackate may be directly used for many purposes, it is preferably given at least a flash distillation to remove trace amounts of high molecular weight polymer.

For conversion of the treated cyclooctene crackate to 1,8-dibromooctane, gaseous hydrogen bromide is introduced into the liquid-treated crackate in the presence of a di-t-alkylperoxide, preferably di-t-butylperoxide, while the temperature of the reaction mixture is maintained below about 40 0., preferably below about 25 C. but above about -10 C. Although di-t-alkyl peroxides are remarkably stable towards heat and acids, normally being useful as free radical reaction initiators at temperatures above C., i.e., in the range of 100 to 180 C., they are excellent catalysts for the addition of hydrogen bromide to cyclooctene crackate at temperatures as low as 0 C. and lower. This is especially surprising, in view of the fact that it is known to produce these peroxides in the presence of hydrogen bromide catalyst at much higher temperatures.

Other free radical reaction initiating catalysts may be used in the present process including organic hydroperoxidic, organic azo compounds, as well as free radical generation in the reaction medium by radiant energy irridiation including high energy, high frequency vibrational means, light, electron bombardment and the like. Particularly preferred is the use of di-t-alkyl peroxides as the precursor radical reaction initiating compounds.

In general, hydrogen bromide additions are complete after from about 15 minutes to 8 hours, depending upon the particular free radical catalyst, rate of hydrogen bromide introduction to the reaction zone and temperature. Using di-t-butyl peroxide, having at least a small excess of hydrogen bromide present and at a temperature of 0 C., a reaction time of about two hours is usual. At 25 C., with other conditions being as above, the reaction time required for essentially complete conversion is only about fifteen minutes.

Reaction temperatures appreciably above about 25 C. are undesirable, because ionic side reactions begin to be increasingly favored at higher temperatures. Completion of the reaction is conveniently determined by noting when there is no further sensible take-up of gaseous hydrogen bromide by the reaction medium as by inlet-exit gas flowmeter comparisons and the like.

In the present process, the crude dibromide, as produced above, may be used directly as an intermediate chemical feed for the production of sebaconitrile, sebacic acid and the like.

Representative di-t-alkyl peroxidic organic free radical precursor compounds useful for the initiation of hydrogen bromide addition to the treated cyclooctene crackate of the present process are di-t-butyl, di-t-amyl, di-1,1-dimethylbutyl, di 1,1 dimethyloctyl, di-'1,1-dimethylhexadecyl, di-1,1-dimethyloctadecyl and the like, that is, lower ditertiary-alkyl peroxides as in the general formula:

wherein R and R are alkyl groups having from 1 to 18 carbon atoms and may be the same or different groups.

Other organic peroxidic catalysts useful in the process are benzoyl peroxide, lauroyl peroxide, bis-p-chlorobenzoyl peroxide, di-l-naphthoyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone hydroperoxide, t-butyl perbenzoate, cumene hydroperoxide, cyclohexyl hydroperoxide, diisopropylperoxydicarbonate, 2-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, decalin hydroperoxide and the like.

Efiective catalytic amounts of these and the above noted preferred organic free radical initiators useful in the process vary but in general are in the range 0.1 to 10 mol percent based upon the crackate feed.

Example 1 A heart-cut aliquot (98.5 parts) of liquid cyclooctene crackate having a boiling point range of 118 to 121 C. at 760 mm. of Hg pressure was thoroughly mixed with 1.5 parts of 90% aqueous sulfuric acid (10 parts H O:90 parts H 80 while maintaining the temperature of the resulting mixture below about 5 C. After less than 5 minutes contact time, the crackate was separated from the acid phase by decantation and the hydrocarbon was washed with water, 5% aqueous sodium hydroxide solution and again fresh water. After drying, the crackate was flash distilled, leaving a small amount of polymeric bottoms, i.e., 1,7-octadiene recovery was greater than about 96%.

HYDROBROMINATION Example 2 In a closed reactor system having a gas inlet and outlet fitted for stirring and temperature control, separate aliquots of the treated and untreated cyclooctene crackate of Example 1 were contacted with essentially anhydrous hydrogen bromide as follows:

When the treated diolefin feed was hydrobrominated at about C., the conversion was quantitative and the product was for all practical purposes 100% 1,8-dibromooctane.

From the foregoing examples, it is seen that the sulfuric acid treatment essentially completely eliminates the catalytic material responsible for byproduct formation in the addition of hydrogen bromide to the cyclooctene crackate feed. Reaction times for the treated feed are 33 /3 faster, and the product is of a premium reagent grade.

For the satisfactory treatment of the crackate, small amounts of water appear to be required in the sulfuric acid. On the other hand, large amounts of water in the acid, i.e., of the order of 15% and more, appear to favor polymerization and isometrization of the diene. In general, about 8897% sulfuric acid is useful. Preferably, from about 0.5 to parts per 100 parts of diene of 90 95% sulfuric acid are employed in the treatment at liquid phase contacting temperatures below about C. and above the freezing point of the mixture.

The advantages of the present process are further illustrated in the following example where the resulting dibromide was converted to nitrile as follows:

CYANOLYSIS Example 3 Aliquots of hydrobrominated, treated and untreated crackate feed were analogously converted as described in the following section, and the corresponding nitrile product recovered:

The foregoing data show that the untreated crackate feed is unsatisfactory for sebaconitrile production.

In making the above conversions of the noted dibromide feeds to nitrile it was necessary to employ particular high molecular weight u,w-dibromoalkane solvolytic conditions.

CYANOLYTIC MEDIA Example 4.

Satisfactory results in the cyanolysis of 1,8-dibromooctane are contingent upon the use of a particular type solvent medium. This is demonstrated in the runs listed in Table I following, carried out under the following conditions:

Temperature reflux:

Satisfactory solvents for the cyanolysis of 1,8-dibromooctane are, in general, water-lower carbinol mixtures. At least about 1 weight percent of Water must be miscible in the carbinol in the cyanolysis temperature range, i.e., from about 25-150 C. Ethanol is preferred. By lower carbinol, ROH, is meant carbinols in which R is, in general, n-alkyl, cycloalkyl, branched-chain alkyl and the like having from 1 to about 10 carbon atoms per alkyl group.

In general, miscible carbinol-Water cyanolysis media useful in the process should contain from about 1-45 parts of water per parts of the medium. Preferably, Water contents are in the range 10-45 parts per 100.

In addition to the carbinols listed in Table I above, others which may be used are t-butanol, cyclohexanol, isobutanol, pentanols and the like.

By high molecular weight a,w-dibromoalkane cyanolysis conditions is meant the contacting for periods of from 0.1 to 8 hours of 1,8-dibromooctane or a higher dibromoalkane analog up to about a C molecular weight with a monovalent cationic cyanide in the presence of a miscible lower carbinol-Water cyanolysis mixture at a temperature in the range 25-150 C. in which the relative amount of cyanide salt and organic dibromide is of the order of the stoichiometric requirement up to about 1.5 fold excess of salt. The above solvent mixture necessarily has from about l-45 parts of water per 100 parts of said cyanolysis mixture.

Under the above conditions, reaction times of from 20 minutes or less up to about 2.5 hours are enjoyed. Otherwise, no appreciable conversion or reaction times of at least 5 hours and longer result.

Under preferred high molecular Weight, i.e., from about C to C weight range, a,w-dibromoalkane cyanolysis conditions, from at least a stoichiometric up to about 10 mol percent excess amount of an alkali metal cyanide,

for example, sodium cyanide, is contacted with the dibromoalkane in the presence of about a 57% aqueous ethanolic solvent (i.e., 57 volumes of ethanol plus 43 volumes of water).

The shorter reaction times obtain when the reaction is accomplished in a pressure autoclave, for example, at about 100 C., and the longer, 2.5 hours reaction time, obtains when atmospheric pressure reflux temperatures are maintained.

The above cyanolysis examples demonstrate that higher molecular weight normal u,w-alkadienes can be efiiciently converted to a,w-dicyanoalkanes under the hydrobromination and cyanolysis conditions of the present process. By higher molecular weight alkadienes is meant those normal dienes of molecular weights reasonably approximate to 1,7-octadiene, such as 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene on up to about 1,15-hexadecadiene and mixtures thereof.

The foregoing descriptive embodiments of the present invention are illustrative only. It is not the intent that the invention shall be construed as limited to the details of the above description, except insofar as such limitations have been included in the terms of the following claims.

We claim:

1. Process for the production of normal a,w-dicyanoalkane having from to 18 carbon atoms per molecule which comprises:

(a) hydrobrominating an unsubstituted normal oc,w-

alkadiene having from 8 to 18 carbon atoms per molecule by reacting in the liquid phase for a period of from 0.25 to 8 hours said diene with hydrogen bromide at a temperature in the range 10 to 40 C. in the presence of a lower di-tertiary-alkyl peroxide, said peroxide being selected from the group of the general formula:

(3H3 CH3 R1COO( 3-Ra (5H3 H3 wherein R and R are alkyl groups having from 1 to 18 carbon atoms; and

(b) reacting at a temperature in the range from about 25 to 150 C. and for a period in the range from 0.1 to 8 hours said hydrobrominated alkadiene with a monovalent cationic cyanide salt in a solution reaction wherein the solvent comprises a miscible mixture of water and a lower carbinol, said mixture containing for each 100 parts from about 1 to parts of water, and wherein said reaction mixture contains from about 2 to 3 mols of salt per mol of dibromide, thereby producing the corresponding o dicyanoalkane.

2. Process of claim 1 wherein said carbinol co-solvent is ethanol and said reaction medium contains from 10 to 45 parts of water and from to parts of said carbinol per parts of solvent mixture.

References Cited UNITED STATES PATENTS 3,005,845 10/1961 Bain 260663X 3,190,909 2/1965 Inaba et al. 260465.8

FOREIGN PATENTS 453,541 12/1948 Canada.

OTHER REFERENCES German printed application 1,134,362, 8-1962.

CHARLES B. PARKER, Primary Examiner. I. P. BRUST, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,329,704 July 4 1967 Charles V. Goebel, Jr. et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification, lines 4 to 6,for "Charles V. Goebel Jr. 17 Constitution Drive Corte Madera, Calif. 94925, and Louis L. Ferstadig, 2548 Tas'sajara Ave. El Cerrito, Calif. 94530" read Charles V. Goebel, Jr., Corte Madera, Clif. and Louis L. Ferstandig, El Cerrito, Calif. assignors to \flhevr-on Research Company, San Francisco, Calif. a corporation of Delaware Signed and sealed this 15th day of July 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents 

1. PROCESS FOR THE PRODUCTION OF NORMAL X,W-DICYANOALKANE HAVING FROM 10 TO 18 CARBON ATOMS PER MOLECULE WHICH COMPRISES: (A) HYDROBROMINATING AN UNSUBSTITUTED NORMAL X,WALKADIENE HAVING FROM 8 TO 18 CARBON ATOMS PER MOLECULE BY REACTING IN THE LIQUID PHASE FOR A PERIOD OF FROM 0.25 TO 8 HOURS SAID DIENE WITH HYDROGEN BROMIDE AT A TEMPERATURE IN THE RANGE - 10 TO 40*C. IN THE PRESENCE OF A LOWER DI-TERTIARY-ALKYL PEROXIDE, SAID PEROXIDE BEING SELECTED FROM THE GROUP OF THE GENERAL FORMULA: 